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CN109715679A - Coating composition, method of producing organic electroluminescent device using the same, and organic electroluminescent device produced thereby - Google Patents

Coating composition, method of producing organic electroluminescent device using the same, and organic electroluminescent device produced thereby Download PDF

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Publication number
CN109715679A
CN109715679A CN201780057021.9A CN201780057021A CN109715679A CN 109715679 A CN109715679 A CN 109715679A CN 201780057021 A CN201780057021 A CN 201780057021A CN 109715679 A CN109715679 A CN 109715679A
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electrode
light emitting
emitting diode
transport layer
organic light
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CN109715679B (en
Inventor
尹锡喜
李载澈
金填硕
李东龟
金禾景
郑在学
申旨娟
金大虎
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LG Chem Ltd
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    • H10K85/10—Organic polymers or oligomers
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    • C09D141/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Coating compositions based on derivatives of such polymers
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    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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Abstract

The present specification relates to a hole injection or transport layer coating composition for an organic light emitting diode, which comprises an organometallic complex of a transition metal, a fluorine-based polymer containing sulfonic acid or sulfonate, and an organic solvent, a method of manufacturing an organic light emitting diode using the same, and an organic light emitting diode using the same.

Description

Application composition produces the method for organic electroluminescence device using it and thus gives birth to The organic electroluminescence device of production
Technical field
This specification requires the South Korea patent application 10- submitted on November 7th, 2016 to Korean Intellectual Property Office No. 2016-0147558 priority and right, entire contents are incorporated herein by reference.
This specification is related to application composition, the method for manufacturing Organic Light Emitting Diode and using the organic of its manufacture Light emitting diode.
Background technique
Organic light emission phenomenon is one of the example for converting electrical current into visible light by the internal procedure of specific organic molecule. The principle of organic light emission phenomenon is as follows.When organic material is placed between anode and cathode and is applied between two electrodes When electric current, electrons and holes are injected into organic material layer from cathode and anode respectively.The electronics being injected into organic material layer With hole-recombination to form exciton, and shine when these excitons are dropped back into ground state.Utilize the organic light emission two of this principle Pole pipe usually can by cathode, anode and be placed in therebetween organic material layer (for example including hole injection layer, hole transmission layer, The organic material layer of luminescent layer and electron transfer layer) it is formed.
When using vacuum method manufacture Organic Light Emitting Diode, high equipment investment cost and work are had the disadvantage in that The burden of skill cost is very high, by device uniformly expand have limitation, and due to during deposition material be wasted rather than The high percentage being deposited in substrate, so the utilization rate of material is low.Meanwhile when use solwution method manufactures Organic Light Emitting Diode When, there are following advantages: can reduce manufacturing cost and large area device easy to manufacture by excluding expensive depositing device Part.However, different from sedimentation, when the layer for forming Organic Light Emitting Diode laminated by solwution method, lower layer is likely to It is formed the process damage on upper layer.In other words, the material of lower layer solvent used in solwution method or ink dissolve again, cause with The phenomenon that upper layer mixes or damages thin film physics.Such phenomenon in order to prevent, the solvent used in each layer use For each other do not have dissolubility, or can also increase by post-process to lower layer prevent lower layer formation upper layer Shi Rong The process of solution.
In the Organic Light Emitting Diode manufactured using such solwution method method, most-often used hole injection layer material It is conducting polymer.These conducting polymers itself do not have highly dissoluble, and usually with the form of aqueous solution, therefore, As solvent properties be different from upper layer used in organic solvent, so ensuring machinability to a certain extent.In addition, working as When using these conducting polymers, relatively low operation voltage is obtained.However, these conducting polymers are low usually using having The acidic dopant material of pH and the electrode material for damaging lower layer, and therefore have the shortcomings that deteriorate life characteristic.Meanwhile As another method for forming hole injection layer, it is known that by the way that ionic material or n-type material (such as TCNQ) are doped to base The forming method carried out in the material of arylamine.However, as described above, this method still has the rear place to solvent or ink The problem of managing tolerance.
Summary of the invention
Technical problem
This specification be intended to provide can be used when manufacturing Organic Light Emitting Diode using solwution method for coating sky The composition of cave injection or transport layer manufactures the method for Organic Light Emitting Diode using it and using the organic light emission two of its manufacture Pole pipe.
Technical solution
One embodiment of this specification provides the hole injection or transport layer coating combination of Organic Light Emitting Diode Object,
The composition includes:
The organometallic complex of transition metal；
The polymer of unit containing following formula 1；With
Organic solvent:
[chemical formula 1]
In chemical formula 1,
A is the alkylidene for being substituted or being unsubstituted, and replaces at least one C of alkylidene chain and can have aromatics Hydrocarbon ring, heterocycle, O, S, C (=O), S (=O) or S (=O)2,
X1For O or S, X2For CR5R6, O or S, n be integer of 1 to 10, p is integer of 1 to 10, and m be 0 to 10 it is whole Number,
Y is SO3H、SO3Li、SO3Na、SO3K、SO3Rb or SO3Cs, and
R1To R6It is each independently hydrogen, fluorine, alkyl or fluoroalkyl, however, R1And R2At least one of be fluorine.
This specification another embodiment provides the methods for manufacturing Organic Light Emitting Diode comprising:
Prepare substrate；
First electrode is formed on the substrate；
One or more organic material layers are formed on the first electrode；And
Second electrode is formed on organic material layer,
And further include by using according to the coating method of the application composition of the embodiment above first electrode with Hole injection or transport layer are formed between organic material layer or between second electrode and organic material layer.
This specification another embodiment provides Organic Light Emitting Diodes comprising:
First electrode；Second electrode；And one or more organic materials being arranged between first electrode and second electrode The bed of material,
And further include hole injection or transport layer, the hole injection or transport layer are arranged in first electrode and organic material Between the bed of material or between second electrode and organic material layer, and use the application composition shape according to the embodiment above At.
This specification another embodiment provides Organic Light Emitting Diodes comprising:
First electrode；Second electrode；And one or more organic materials being arranged between first electrode and second electrode The bed of material,
And further include hole injection or transport layer, the hole injection or transport layer are arranged in first electrode and organic material It between the bed of material or between second electrode and organic material layer, and include transition metal oxide and containing chemical formula 1 The polymer of unit.
Beneficial effect
In the present specification, organic polymer and transition metal with both sulfonic acid or sulfonate and fluorin radical it is organic Metal complex is used together to form the injection of the hole of Organic Light Emitting Diode or transport layer.Sulfonic acid have oxidability and because This is used as oxidant.Therefore, by sulfonic acid, even if the organic material ligand of organometallic complex is in the indifferent gas of such as nitrogen Be also easy to remove under atmosphere and be successfully converted into metal oxide, and by organic polymer, can coating improved And improved with the interface on upper layer, so as to form more stable hole injection or transport layer, as a result, device may be implemented The long-life of part.In addition, the transition metal oxide such as MoO by keeping high work function3And have sulfonic acid or sulfonate and The organic polymer of fluorin radical maintains the smooth injection properties in hole, and increases and efficiency reduction voltage does not occur In the case of can obtain long-life of device.
Detailed description of the invention
Fig. 1 shows the Organic Light Emitting Diode of an embodiment according to this specification.
Fig. 2 shows can when using the application composition formation film of an embodiment according to present disclosure Determine the XPS result of Mo-Mo key.
101: substrate
201: anode
301: hole injection layer
401: hole transmission layer
501: luminescent layer
601: electron transfer layer
701: cathode
Specific embodiment
Hereinafter, it will be described in this specification.
It in the present specification, not only include that a component adjoining is another by the description that some component is placed in another component "upper" The case where component, and it is included in the case where there are another components between the two components.
In the present specification, non-specifically conversely bright, the otherwise description of certain a part of certain constituent element of " comprising " is removed Mean to include other constituent element, and is not excluded for other constituent element.
In the present specification, " * " means bonding position.
One embodiment of this specification provides the hole injection or transport layer coating combination of Organic Light Emitting Diode Object, the application composition includes: the organometallic complex of transition metal；The polymer of unit containing following formula 1； And organic solvent.
[chemical formula 1]
In chemical formula 1,
A is the alkylidene for being substituted or being unsubstituted, and replaces at least one C of alkylidene chain and can have aromatics Hydrocarbon ring, heterocycle, O, S, C (=O), S (=O) or S (=O)2,
X1For O or S, X2For CR5R6, O or S, n be integer of 1 to 10, p is integer of 1 to 10, and m be 0 to 10 it is whole Number,
Y is SO3H、SO3Li、SO3Na、SO3K、SO3Rb or SO3Cs, and
R1To R6It is each independently hydrogen, fluorine, alkyl or fluoroalkyl, however, R1And R2At least one of be fluorine.
According to an embodiment, in the organometallic complex of transition metal, transition metal is the 3rd race to the 11st race Transition metal.
According to an embodiment, in the organometallic complex of transition metal, transition metal Mo, W, V, Re, Mn Or Rh.
According to another embodiment, the content of the organometallic complex of transition metal is preferably in application composition 0.01 weight % to 50 weight %.In addition, based on the content containing sulfonic acid or the polymer based on fluorine of sulfonate, coating combination The organometallic complex of transition metal preferably exists with 10% or higher content in object.Contain sulfonic acid or sulfonic acid when being used only When the polymer based on fluorine of salt, driving voltage increases a lot and cannot play the role of hole injection or transport layer, however, working as When organometallic complex comprising transition metal, the long-life of device is determined under low driving voltage.
In this embodiment, organometallic complex can be the complex that oxidation number is -2 to+6.Organometallic ligand Closing object includes the organic ligand with above-mentioned metal bonding.Organic ligand is not particularly limited, however it is contemplated that solvent solubility, It is selected with interfacial characteristics of adjacent organic material layer etc..The example of organic ligand may include carbonyl, acetyl group, acetylacetone,2,4-pentanedione Base, methyl acetoacetate base, ethyl acetoacetate base, thiacetate/salt, isocyanates/salt, cyanate/salt, isocyanic acid Ester/salt, halogen atom etc..In addition, organic ligand can have the structure comprising aromatic ring and/or heterocycle, and the example can To include: benzene, triphenylamine, fluorenes, biphenyl, pyrene, anthracene, carbazole, phenylpyridine, three thiophene, phenylDiazole, Phenyltriazole, benzo Imidazoles, phenyl triazine, benzo dithiazine, phenyl quinoxaline, phenylenevinylenes, phenyl thiophene are coughed up or the combination of these structures. Aromatic ring or heterocycle can have substituent group, and for example, substituent group can be alkyl, halogen atom, alkoxy, cyano, nitre Base etc..Alkyl and alkoxy can have such as 1 to 12 carbon atom.
Specifically, the example of organic ligand may include alkoxy or acetic acid esters/salt series, such as acetylacetonate (acac), ethyl acetoacetate, methyl acetoacetate, OPh, carbonyl, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, fourth oxygen Base, sec-butoxy, tert-butoxy, amoxy, hexyloxy, oxygroup in heptan, octyloxy or ethyl hexyl oxy, but not limited to this.In addition, It may include the ligand with these and halogen group together existing form.Organometallic complex can have two kinds of bonding Or more different ligands form.
The example of organometallic complex may include W (CO)6、Mo(CO)6、WO2Cl2、MoO2(acac)2、VO (acac)2、V(acac)3、W(acac)3、WO2(acac)2、MoO2Cl2、ReCl(CO)5Deng.
In one embodiment, the weight average molecular weight of the polymer of the unit containing chemical formula 1 is preferably 2,000 or more Greatly.
In an embodiment of this specification, A is linear or branching the alkylidene for being substituted or being unsubstituted, and And it replaces at least one C of alkylidene chain and can have aromatics hydrocarbon ring, heterocycle, O, S, C (=O), S (=O) or S (=O)2。
According to another embodiment, A is linear or branching the alkylidene for being unsubstituted or replacing through halogen group, and And it replaces at least one C of alkylidene chain and can have aromatics hydrocarbon ring with 6 to 60 carbon atoms, there are 2 to 60 carbon The heterocycle of atom, O, S, C (=O), S (=O) or S (=O)2。
According to another embodiment, A is linear or branching the alkylidene for being unsubstituted or replacing through halogen group, and And it replaces at least one C of alkylidene chain and can have aromatics hydrocarbon ring with 6 to 30 carbon atoms, there are 2 to 30 carbon The heterocycle of atom, O, S, C (=O), S (=O) or S (=O)2。
According to another embodiment, A is to be unsubstituted or fluorine-substituted linear or branching alkylidene, and replace At least one C of alkylidene chain and can have aromatics hydrocarbon ring with 6 to 30 carbon atoms, with 2 to 30 carbon atoms Heterocycle, O, S, C (=O), S (=O) or S (=O)2。
In another embodiment, A is to be unsubstituted or fluorine-substituted linear or branching alkylidene, and replace At least one C of alkylidene chain and can have aromatics hydrocarbon ring, O or C (=O) with 6 to 30 carbon atoms.
In another embodiment, A is to be unsubstituted or fluorine-substituted linear or branching alkylidene, and replace At least one C of alkylidene chain and can have benzene, O or C (=O).
In an embodiment of present disclosure, when replacing at least one C of alkylidene chain of A and there is benzene, Bonding is the form of divalent phenyl group, and bonding is the form of-O- when with O, and bonding is-C (=O)-when with C (=O) Form.
According to another embodiment, it is fluorine-substituted that at least one carbon of alkylidene is formed in A.According to another Embodiment, chemical formula 1 can be indicated by following formula 1-1 or 1-2.
[chemical formula 1-1]
[chemical formula 1-2]
In chemical formula 1-1 and 1-2, q, r, s and t mean the molal quantity in each bracket and be 1 to 500 integer, And remaining substituent group is identical as defined in chemical formula 1.
According to an embodiment, in chemical formula 1,1-1 and 1-2, R1And R2It is each independently fluorine or fluoroalkyl.
According to another embodiment, in chemical formula 1,1-1 and 1-2, R1And R2It is each independently fluorine or CF3。
According to another embodiment, in chemical formula 1,1-1 and 1-2, X1For O or S.
According to another embodiment, in chemical formula 1,1-1 and 1-2, X2For O or CR5R6。
In another embodiment, in chemical formula 1,1-1 and 1-2, R5And R6For fluorine.
According to another embodiment, in chemical formula 1,1-1 and 1-2, X2For O or CF2。
In another embodiment, in chemical formula 1,1-1 and 1-2, R3And R4It is each independently fluorine.
According to another embodiment, in chemical formula 1,1-1 and 1-2, it is 0 or 1 that n and p, which are 2, m, and when n and p is each From when being 2, the structure in bracket is same or different to each other.
According to an embodiment, in chemical formula 1,1-1 and 1-2, Y SO3H or SO3K。
This disclosure relates to be used to form the application composition of the injection of the hole of Organic Light Emitting Diode or transport layer, and And by the inclusion of organometallic complex, the polymer and organic solvent based on fluorine containing sulfonic acid or sulfonate, formed uniform Film and therefore can manufacture the device with low driving voltage, high efficiency and excellent lifetime characteristic.At the same time it can also examine Consider by using the nano particle such as MoO by dispersion with high work content numerical value3Or WO3And the application composition prepared forms sky The method of cave injection and transport layer, however, being the shortcomings that nano particle: during purification process in post synthesis frequent occurrence The phenomenon that grain aggregation, and be difficult to prepare uniform and stable dispersion application composition.
In addition, even if when the application composition comprising nano particle is evenly dispersed, during drying process after application It also can there is a phenomenon where particles to reassociate, as a result, be difficult to obtain uniform coated film.Meanwhile nanometer is being used in order to improve Dispersibility when grain can add carboxylic acid or the amine for the long chain type alkyl for being about 8 to 20 with carbon atom to prevent particle poly- Collection, however, in such a case, it is possible to determination, serves as insulator, device for example, by the additive of amine or carboxylic acid between particles The driving voltage of part increases.
Meanwhile in the application composition of present disclosure, organometallic complex and the base containing sulfonic acid or sulfonate It is completely dissolved in the polymer of fluorine and exists in a solvent rather than in the form of dispersion liquid, it therefore, can be with when forming coated film Uniform film is obtained without will lead to rendezvous problem.
In one embodiment, the weight average molecular weight of the polymer of the unit containing chemical formula 1 is preferably greater than or waits In 2,000 and be less than or equal to 2,000,000.When the molecular weight of the material is less than 2,000, in coating, film forms shakiness It is fixed, and the effect for improving device property is smaller.When molecular weight is greater than 2,000,000, viscosity of material becomes too high, leads to difficulty To form lubricious problem.
In one embodiment, relative to entire application composition, the content of polymer be preferably 0.01 weight % extremely 50 weight %.With regard to film can coating improve and device long-life for, polymer, which is not included in application composition, is It is undesirable, and content be greater than 50 weight % be not suitable for being formed with machine light-emitting diodes due to excessively high concentration it is effective thin The coating method of film.
In one embodiment, organic solvent is not particularly limited, but including ethers, alcohols, ketone and esters solvent One or more of seed types.
In one embodiment, organic solvent includes alcohols solvent.
In another embodiment, organic solvent includes esters solvent.
In another embodiment, organic solvent includes ether solvent.
In another embodiment, organic solvent includes ketones solvent.
In the present specification, organic solvent may include one of following: tetrahydrofuran, acetone, methyl ethyl ketone, two Ethyl ketone, cyclohexanone, cyclopentanone, isophorone, acetylacetone,2,4-pentanedione, tetralone, ethyl benzoate, methyl benzoate, benzoic acid Butyl ester, ethyl acetate, ethyl acetoacetate, acetoacetate diethylester, methyl benzoate, ethyl benzoate, methanol, ethyl alcohol, third Alcohol, isopropanol, butanol, sec-butyl alcohol, the tert-butyl alcohol, amylalcohol, cyclopentanol, hexanol, cyclohexanol, enanthol and octanol, and can serve as reasons The solvent that following formula 5 indicates.
[chemical formula 5]
In chemical formula 5, n is integer of 1 to 20, the integer that l and m are respectively or simultaneously 0 to 5, R1、R2、R3And R4 It is respectively or simultaneously hydrogen atom, the alkyl with 1 to 20 carbon atom, the alkenyl with 2 to 20 carbon atoms, has 2 To the alkynyl of 20 carbon atoms, the alkoxy with 1 to 20 carbon atom, the aryl with 6 to 40 carbon atoms, have 2 to The heteroaryl of 40 carbon atoms or ester group with 1 to 20 carbon atom.
According to an embodiment, the boiling point of organic solvent is preferably 350 DEG C or lower.Its specific example may include second Glycol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol Monohexyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, butyl cellosolve, ethylene glycol diamyl ether, second two Two hexyl ether of alcohol, 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,2- butanediol, 1,3 butylene glycol, diethylene glycol (DEG), diethyl two Alcohol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, ethylene acetate, PEG 600, triethylene glycol etc..
The solvent indicated by chemical formula 5 does not form chemistry with the organometallic complex for being used as transition metal oxide precursor Strong bond, but prevent the precursor from easily becoming other oxidation state or material, and therefore have and produce after manufacturing device not The advantages of leaving the sull of organic substance.
Other than organometallic complex, application composition can also for example coat spy comprising additive to improve characteristic Property and viscosity.For example, additive may include it is selected from the following any one or more person: dispersing agent, surfactant, polymerization It is object, adhesive, cross-linked binder, emulsifier, defoaming agent, desiccant, filler, incremental agent, thickener, film regulator, anti-oxidant Agent, free-flow agents, levelling additive and corrosion inhibitor.
Another embodiment of this specification is related to the method for manufacturing Organic Light Emitting Diode, and the method Include:
Prepare substrate；
First electrode is formed on the substrate；
One or more organic material layers are formed on the first electrode；And
Second electrode is formed on organic material layer,
And further include by using according to the coating method of the application composition of the embodiment above first electrode with Hole injection or transport layer are formed between organic material layer or between second electrode and organic material layer.
Formed hole injection or transport layer coating method can for for example it is selected from the following any one: spin-coating method, ink-jet Method, nozzle print, wet coating, spraying, scraper coating, contact printing, top charging reverse printed, lower part charging reverse printed, spray Mouth feed reverse printed, intaglio printing, dimple version printing, reversed dimple version printing, roller coating, slit die coating, capillary coating, Jet deposition and sprayed deposit, and can be preferably spin coating, ink-jet coating, nozzle print etc..
Coating can by by above-mentioned composition be coated in first electrode or second electrode and dry gains come into Row.Dry and heat treatment or heat treatment after drying can carry out under a nitrogen or in an atmosphere, however, in an atmosphere It carries out being conducive to remove solvent and organic material ligand, and is conducive to convert oxide for organometallic complex.In addition, About heat treatment, treatment temperature can change according to used organometallic complex, but can be 150 DEG C or more Height, and preferably 200 DEG C or higher.
According to an embodiment, the hole injection that is formed using application composition or transport layer with a thickness of 1nm to 1, 000nm.In general Organic Light Emitting Diode, due to chamber effect, the thickness to entire device is needed to optimize, and When optimizing thickness, thickness needs micron variation from several nanometers to 1 according to upper layer of material.Here, when can change charge injection or When transport layer thickness is without making device characteristic deterioration, the limitation of upper device structure and thickness change is reduced, this is conducive to mention For the device property of optimization.The hole injection provided in present disclosure or transport layer increase almost without the voltage as caused by thickness Add.
According to another embodiment, manufacturing method further include formed using application composition formed hole injection or It anneals after transport layer.Annealing can 150 DEG C to 250 DEG C at a temperature of carry out.In this disclosure, annealing is intended to The organic ligand of organometallic complex is removed and is become metal oxide in annealing process, and therefore, temperature is preferably It is enough the high temperature for decomposing the ligand of organometallic complex, and atmosphere preferably has the atmosphere of oxygen to become to aoxidize Object.
It mixes as in embodiment described in this specification and is provided containing the polymer of sulfonic acid or sulfonate and fluorine The advantage that: since even if the oxidation promotion functions of sulfonic acid or sulfonate also obtain be heat-treated in a nitrogen atmosphere Must have the device of low driving voltage and long-life.
In this embodiment, in addition to hole injection or transport layer using the application composition according to the embodiment above come Except formation, the material and preparation method of other electrodes and organic material layer can be used it is as known in the art those.
According to an embodiment, first electrode is anode and second electrode is cathode.
According to another embodiment, second electrode is anode and first electrode is cathode.
According to an embodiment, organic material layer includes luminescent layer.
According to another embodiment, organic material layer can be formed as multilayered structure, and for example may include shining Layer and at least one of the following layer: hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer, electronic barrier layer And hole blocking layer.For example, shown in Figure 1 according to the structure of the Organic Light Emitting Diode of this specification embodiment.
Fig. 1 shows the structure of Organic Light Emitting Diode, wherein in succession laminated on substrate (101) have anode (201), sky Cave implanted layer (301), hole transmission layer (401), luminescent layer (501), electron transfer layer (601) and cathode (701).In Fig. 1, Above-mentioned application composition can be used to be formed in hole injection layer (301).However, Fig. 1 shows Organic Light Emitting Diode, and Organic Light Emitting Diode is without being limited thereto.
When Organic Light Emitting Diode includes a plurality of organic material layers, organic material layer can be by being same or different to each other Material formed.
For example, the Organic Light Emitting Diode of this specification can pass through successive layer Heyang pole, organic material layer in substrate It is manufactured with cathode.Here, Organic Light Emitting Diode can be such as manufacture of getting off: (such as being splashed using physical vapour deposition (PVD) (PVD) method Penetrate or electron beam evaporation plating) deposited metal, conductive metal oxide or its alloy and anode is formed on the substrate, in sun Extremely upper formation includes the organic material layer of hole injection layer, hole transmission layer, luminescent layer and electron transfer layer, then in organic material Deposition can be used as the material of cathode on the bed of material.Other than such method, Organic Light Emitting Diode can also be by base Sequential deposition cathode material, organic material layer and anode material manufacture on bottom.Here, being present between anode and cathode extremely A few layer or all layers can be used solwution method and formed.The example of solwution method may include printing process, such as ink jet printing, Nozzle print, hectographic printing, transfer or silk-screen printing, but not limited to this.When manufacturing device, using solwution method the time and at Present aspect is cost-effective.When forming organic material layer using solwution method, as needed, can be heat-treated with further progress Or light processing.Here, heat treatment temperature and time can select according to process condition or the material used, for example, heat treatment It can be carried out 1 minute to 1 hour at 85 DEG C to 300 DEG C.
As anode material, it is usually preferred to the material with big work function, so that hole is successfully injected into organic material Layer.The specific example that can be used in the anode material of present disclosure includes: metal, such as vanadium, chromium, copper, zinc and gold or its conjunction Gold；Metal oxide, such as the tin oxide of zinc oxide, indium oxide, tin indium oxide (ITO), indium gallium zinc (IGZO), Fluorin doped (FTO) and indium zinc oxide (IZO)；The combination of metal and oxide, such as ZnO:Al or SnO2:Sb；Conducting polymer, for example, it is poly- (3 methyl thiophene), poly- [3,4- (bis- oxygroup of ethylidene -1,2-) thiophene] (PEDOT), polypyrrole and polyaniline, but be not limited to This.
As cathode material, it is usually preferred to the material with small work function, so that electronics is successfully injected into organic material Layer.The specific example of cathode material includes: metal, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminium, silver, tin and lead, or Its alloy；Sandwich, such as LiF/Al or LiO2/Al；Etc., but not limited to this.
It is being formed except the hole injection formed using the above-mentioned application composition comprising organometallic complex or transport layer Except other hole injection layer when, the preferably such compound of hole injection layer material: its energy with transporting holes Power, therefore with the hole injection effect in anode, there is excellent hole injection effect to luminescent layer or luminescent material, prevent The exciton generated in luminescent layer is moved to electron injecting layer or electron injection material, and in addition to this, with excellent thin Film Forming ability.The highest occupied molecular orbital (HOMO) of hole-injecting material preferably has with around in the work function of anode material Between the HOMO of machine material layer.The specific example of hole-injecting material includes metalloporphyrin, Oligopoly thiophene, having based on arylamine Machine material, the organic material based on six nitriles, six azepine benzophenanthrene, the organic material based on quinacridone, based on organic material Material, anthraquinone and based on polyaniline and the conducting polymer based on polythiophene etc., but not limited to this.
Hole transmission layer is to receive the hole from hole injection layer and by the layer of hole transport to luminescent layer, and conduct Hole mobile material, such material are suitable: it can receive the hole from anode or hole injection layer, and hole is moved It moves to luminescent layer, and there is high hole mobility.Its specific example includes organic material, conducting polymer based on arylamine Object has block copolymer of conjugate moiety and non-conjugated portion etc. simultaneously, but not limited to this.
Emitting layer material be can by receive respectively from hole transmission layer and electron transfer layer hole and electronics simultaneously Make hole and electronics in conjunction with and issue the material of the light in visible light region, and preferably there is advantageous amount to fluorescence or phosphorescence The material of sub- efficiency.Its specific example includes: 8-hydroxyquinoline aluminum complex (Alq3)；Compound based on carbazole；Two polyphenyl Vinyl compound；BAlq；10- hydroxy benzo quinoline-metallic compound；Based on benzoAzoles based on benzothiazole and is based on The compound of benzimidazole；Polymer based on poly- (to phenylene vinylidene) (PPV)；Spiro-compound；Polyfluorene, rubrene Deng, but not limited to this.
Luminescent layer may include material of main part and dopant material.Material of main part includes fused aromatic ring derivatives, containing miscellaneous The compound etc. of ring.Specifically, fused aromatic ring derivatives include anthracene derivant, pyrene derivatives, naphthalene derivatives, pentacene derivative Object, phenanthrene compound, fluoranthene compound etc., and the compound containing heterocycle includes carbazole derivates, dibenzofuran derivative, ladder Type furan compound, pyrimidine derivatives etc., but material is without being limited thereto.
Dopant material includes that aromatic amine derivative, styrylamine compound, boron complexes, fluoranthene compound, metal are matched Close object etc..Specifically, aromatic amine derivative is the fused aromatic ring derivatives with the arylamino for being substituted or being unsubstituted, And including the pyrene containing arylamino, anthracene,Two indeno pyrenes etc., styrylamine compound are wherein substituted or without taking The compound that the arylamine in generation replaces through at least one aryl vinyl, and it is selected from aryl, silicyl, alkyl, naphthenic base It is substituted or is unsubstituted with the one, two or more substituent group in arylamino.Specifically, including styrene Amine, styrene diamines, styrene triamine, styrene tetramine etc., but styrylamine compound is without being limited thereto.In addition, metal combination Object includes complex of iridium, platinum complex etc., but not limited to this.
Electron transfer layer is to receive the electronics from electron injecting layer and by the layer of electron-transport to luminescent layer, and conduct Electron transport material, such material are suitable: it can advantageously receive the electronics for carrying out cathode, electronics is moved to luminous Layer, and there is high electron mobility.Its specific example includes: the Al complex of 8-hydroxyquinoline；Include Alq3Complex； Organic free radical compound；Flavonol-metal complex；Etc., but not limited to this.Electron transfer layer can be with such as this field Used in any desired cathode material be used together.Particularly, the example of suitable cathode material includes having small function Function and the common materials for being wherein followed by aluminium layer or silver layer.Specifically, cathode material includes caesium, barium, calcium, ytterbium and samarium, and It is all followed by aluminium layer or silver layer in each case.
Electron injecting layer is the layer for the electronics that injection carrys out self-electrode, and electron injection material is preferably such chemical combination Object: it has the ability of transmission electronics, has the electron injection effect from cathode, has to luminescent layer or luminescent material excellent Electron injection effect, prevent the exciton generated in luminescent layer to be moved to hole injection layer, and in addition to this, have it is excellent Film Forming ability.Its specific example include Fluorenone, anthraquinone bismethane, diphenoquinone, thiopyrandioxide,Azoles,Two Azoles, triazole, imidazoles, tetrabasic carboxylic acid, fluorenylidene-methane, anthrone etc. and its derivative, metal complex compounds, nitrogenous 5 member ring Derivative etc., but not limited to this.
Metal complex compounds include 8-hydroxyquinoline lithium, bis- (8-hydroxyquinoline) zinc, bis- (8-hydroxyquinoline) copper, double It is (8-hydroxyquinoline) manganese, three (8-hydroxyquinoline) aluminium, three (2- methyl -8-hydroxyquinoline) aluminium, three (8-hydroxyquinoline) galliums, double (10- hydroxy benzo [h] quinoline) beryllium, bis- (10- hydroxy benzo [h] quinoline) zinc, bis- (2- methyl -8- quinoline) chlorine galliums, bis- (2- first Base -8- quinoline) (o-cresol) gallium, bis- (2- methyl -8- quinoline) (1- naphthols) aluminium, bis- (2- methyl -8- quinoline) (beta naphthal) galliums Deng, but not limited to this.
Hole blocking layer is the layer for stopping hole to reach cathode, and usually can be in condition identical with hole injection layer Lower formation.Specifically, includingOxadiazole derivative or triazole derivative, phenanthroline derivative, BCP, aluminum complex etc., but material Expect without being limited thereto.
This specification another embodiment provides Organic Light Emitting Diodes comprising: first electrode；Second electricity Pole；And one or more organic material layers being arranged between first electrode and second electrode, and further include hole injection Or transport layer, hole injection or transport layer be arranged between first electrode and organic material layer or second electrode with have Between machine material layer, and uses and formed according to the application composition of the embodiment above.
The hole injection formed using application composition or transport layer comprising transition metal oxide and contain above-mentioned chemistry The polymer of the unit of formula 1.By the inclusion of the polymer based on fluorine as above containing sulfonic acid or sulfonate, low point can be improved The stability and uniformity of the coated film of son amount Organotransitionmetal complex.Particularly, by with it is described in this specification Polymer is included together, and can also provide in the devices makes to play a crucial role in terms of the service life for reducing organic luminescent device Moisture or oxygen minimize the advantages of.In addition, when use it is described in this specification containing sulfonic acid or sulfonate based on fluorine Polymer when, high work function (working principle of transition metal oxide) can be kept, and provide improvement and organic material The advantages of interfacial characteristics of layer (upper layer).
The work function of the hole injection or transport layer that are formed using application composition is big for 5.5eV or more.
According to an embodiment, the hole injection that is formed using application composition or transport layer with a thickness of 1nm to 1, 000nm。
According to another embodiment, anneal to the hole injection for using application composition to be formed or transport layer.Example Such as, hole injection or transport layer 150 DEG C to 250 DEG C at a temperature of anneal.
According to another embodiment herein, hole injection or transport layer include M-O key and M-M key, or comprising MO3And M2O5, or the interface formation M-O-X key with the adjacent electrode in first electrode and second electrode, and here, M was It crosses metal and X is one of the element of adjacent electrode to be formed in first electrode and second electrode.For example, in MoO3In, when logical When crossing solwution method and forming Mo-Mo key ,+5 oxidation number is also obtained other than+6 oxidation number, and as shown in Figure 2, it can be with It determines, when analyzing using XPS the film obtained by solwution method, detects that oxidation number is+5 (lower oxidation numbers) The peak Mo.Here, the amount for the Mo that oxidation number is+5 is not particularly limited, as long as it is greater than 0.As another embodiment party Case, hole injection or the adjacent first electrode formed by ITO of transport layer, and M-O-In is being formed with the interface of first electrode Or M-O-Sn key.
For example, when forming M-O-X key as above between electrode and hole injection layer film, adhesive strength enhancing, and And the mechanical strength of hole injection layer itself can increase.
About other compositions of Organic Light Emitting Diode, description provided above and structure known in the art can be applied At.
According to used material, top emission type can be according to the Organic Light Emitting Diode of this specification, bottom is sent out Emitting or dual emission type.
Invention embodiment
Hereinafter, this specification will be described in detail referring to embodiment to specifically describe this specification.However, according to this theory The embodiment of bright book may be modified as a variety of different forms, and the range of this specification should not be construed as limited to it is following The embodiment of description.The embodiment of this specification is provided to be described more fully this explanation to those of ordinary skill in the art Book.
Embodiment 1.
It, will be by making MO after washing the substrate of glass coated with ITO with water and isopropanol in succession2(acac)2With Nafion (following structural formula A) mixed with the ratio of 9:1 and gains are dissolved in the solution obtained in glycol monoethyl ether with 3000rpm is spin-coated in the substrate for be deposited with ITO 30 seconds.Hot place is carried out to the film of acquisition at 200 DEG C under oxygen atmosphere Reason 15 minutes, to form the highly uniform hole injection layer with a thickness of 30nm.
On the top of hole injection layer, by the way that the hole mobile material indicated by following below formula B is dissolved in toluene In, using spin-coating method formed with a thickness ofHole transmission layer.
On the hole transport layer, by the way that blue dopant BD is doped into blue-fluorescence main body BH with the weight ratio of 95:5 Come formed with a thickness ofLuminescent layer.
Then, on the top of luminescent layer, then the material by depositing following below formula C deposits LiF to form electronics Transport layer and electron injecting layer.
Finally, depositing Al is extremely on LiF layerThickness to manufacture Organic Light Emitting Diode.The characteristic of the device It is shown in Table 1.
Chemical formula C
Embodiment 2.
Manufacture device in the same manner as in example 1, the difference is that in a nitrogen atmosphere to film at Reason.
Embodiment 3.
Device is manufactured in the same manner as in example 1, the difference is that using the EW825 (following below formula of 3M D Nafion) is replaced.
Chemical formula D
Embodiment 4.
Manufacture device in the same manner as in example 1, the difference is that using following compound E (Mw=1, 000,000) Nafion is replaced.In following compound E, the ratio of n:m is 2:8.
Compound E
Embodiment 5.
Manufacture device in the same manner as in example 1, the difference is that using following compound F (Mw=500, 000) Nafion is replaced.In following compound F, the ratio of l:m is 1:9.
Compound F
Comparative example 1.
Device is manufactured in the same manner as in example 1, the difference is that MoO is used only2(acac)2Without the use of Additive forms hole injection layer.In this experiment, the life characteristic deterioration of device is determined.
Comparative example 2.
Device is manufactured in the same manner as in example 1, the difference is that Nafion is used only without the use of MoO2 (acac)2To form hole injection layer.Using only Nafion without including organometallic complex (such as MoO2(acac)2) formed Layer show insulating properties.Accordingly, it is determined that the voltage characteristic of manufactured device deteriorates, and its efficiency characteristic and life characteristic Also it deteriorates.
Comparative example 3.
Device is manufactured in the same manner as in example 1, the difference is that by polystyrolsulfon acid (molecular weight: Mw =75,000) (following below formula G) is mixed instead of Nafion.
Chemical formula G
In this experiment, even if determining when using sulfonic acid, voltage characteristic deterioration and life characteristic deterioration.
Comparative example 4.
Device is manufactured in the same manner as in example 1, the difference is that replacing using polyvinylphenol Nafion.In this experiment, efficiency characteristic and life characteristic deterioration are determined.
Comparative example 5.
Manufacture device in the same manner as in example 1, the difference is that DuPont Zonyl FSN-100 (with Lower chemical formula H, molecular weight=about 950) purchased from Aldrich and replacement Nafion use.
Chemical formula H
In this experiment, even if adding the material of a large amount of fluoro-containing group, the improvement of coating and device property is not obtained yet.
Comparative example 6.
Device is manufactured in the same manner as in example 1, the difference is that the ratio addition with 9: 1 includes amido Monomer lauryl amine replaces the Nafion comprising sulfonyl.In this experiment, observe that coating characteristic is relatively non-uniform existing As, and observe the phenomenon that driving voltage increases.
Driving voltage, efficiency and the life characteristic of the device manufactured in above-described embodiment and comparative example are shown in table 1 below.
[table 1]
Voltage (V) Efficiency (EQE) LT80
Embodiment 1 4.45 5.05 10
Embodiment 2 4.30 4.95 13
Embodiment 3 4.71 4.32 11
Embodiment 4 4.73 4.5 7
Embodiment 5 4.81 4.53 7.5
Comparative example 1 4.32 4.74 5
Comparative example 2 16.32 3.78 < 0.1
Comparative example 3 6.51 4.38 1
Comparative example 4 4.83 4.08 1
Comparative example 5 X X X
Comparative example 6 6.98 4.46 < 1
Measured value in table 1 is in 10mA/cm2The result of lower measurement.Indicate that the LT80 of life characteristic means that brightness is opposite Reach 80% the time it takes in its original intensity.

Claims (16)

1. a kind of hole of Organic Light Emitting Diode is injected or transport layer application composition, the application composition includes:
The organometallic complex of transition metal；
The polymer of unit containing following formula 1；With
Organic solvent:
[chemical formula 1]
Wherein, in chemical formula 1,
A is the alkylidene for being substituted or being unsubstituted, and replaces at least one C of alkylidene chain and can have aromatic hydrocarbon Ring, heterocycle, O, S, C (=O), S (=O) or S (=O)2；
X1For O or S, X2For CR5R6, O or S, n be integer of 1 to 10, p is integer of 1 to 10, and m is integer of 0 to 10；
Y is SO3H、SO3Li、SO3Na、SO3K、SO3Rb or SO3Cs；And
R1To R6It is each independently hydrogen, fluorine, alkyl or fluoroalkyl, however, R1And R2At least one of be fluorine.
2. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein in institute It states in the organometallic complex of transition metal, the transition metal is the transition metal of the 3rd race to the 11st race.
3. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein in institute It states in the organometallic complex of transition metal, the transition metal is Mo, W, V, Re, Mn or Rh.
4. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein described The content of the organometallic complex of transition metal described in application composition is 0.01 weight % to 50 weight %.
5. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein described The weight average molecular weight of the polymer of unit containing chemical formula 1 is 2,000 or bigger.
6. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein changing In the A of formula 1, it is fluorine-substituted for forming at least one carbon of the alkylidene.
7. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein chemistry Formula 1 is indicated by following formula 1-1 or 1-2:
[chemical formula 1-1]
[chemical formula 1-2]
In chemical formula 1-1 and 1-2, q, r, s and t mean the molal quantity in each bracket and be 1 to 500 integer, and Remaining substituent group is identical as defined in chemical formula 1.
8. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein relatively In entire application composition, the content of the polymer is 0.01 weight % to 50 weight %.
9. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein described Organic solvent includes one or more of seed types of ethers, alcohols, ketone and esters solvent.
10. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein described Organic solvent includes the solvent indicated by following formula 5:
[chemical formula 5]
In chemical formula 5,
N is integer of 1 to 20；
The integer that l and m is respectively or simultaneously 0 to 5；And
R1、R2、R3And R4It is respectively or simultaneously hydrogen atom, the alkyl with 1 to 20 carbon atom, there are 2 to 20 carbon originals The alkenyl of son, the alkoxy with 1 to 20 carbon atom, has 6 to 40 carbon atoms at the alkynyl with 2 to 20 carbon atoms Aryl, the heteroaryl with 2 to 40 carbon atoms or the ester group with 1 to 20 carbon atom.
11. the hole of Organic Light Emitting Diode according to claim 1 is injected or transport layer application composition, wherein described Organic solvent includes at least one of following: ethylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, second Glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexylether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, Butyl cellosolve, ethylene glycol diamyl ether, two hexyl ether of ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,2- Butanediol, 1,3 butylene glycol, diethylene glycol (DEG), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethyl two Alcohol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, ethylene glycol two Acetic acid esters, PEG 600 and triethylene glycol.
12. a kind of method for manufacturing Organic Light Emitting Diode, comprising:
Prepare substrate；
First electrode is formed on the substrate；
One or more organic material layers are formed on the first electrode；
And second electrode is formed on the organic material layer,
It and further include the coating method by using application composition according to any one of claim 1 to 11 in institute It states between first electrode and the organic material layer or forms hole between the second electrode and the organic material layer Injection or transport layer.
13. the method according to claim 12 for manufacturing Organic Light Emitting Diode, wherein being combined using the coating Object formed the hole injection or transport layer with a thickness of 1nm to 1,000nm.
14. the method according to claim 12 for manufacturing Organic Light Emitting Diode further includes using the coating Composition is annealed after forming hole injection or transport layer.
15. a kind of Organic Light Emitting Diode, comprising:
First electrode；
Second electrode；With
One or more organic material layers between the first electrode and the second electrode are set,
And further include hole injection or transport layer, the hole injection or transport layer setting have in the first electrode with described Between machine material layer or between the second electrode and the organic material layer, and using according to claim 1 to 11 Any one of described in application composition formed.
16. a kind of Organic Light Emitting Diode, comprising:
First electrode；
Second electrode；With
One or more organic material layers between the first electrode and the second electrode are set,
And further include hole injection or transport layer, the hole injection or transport layer setting have in the first electrode with described Between machine material layer or between the second electrode and the organic material layer, and includes transition metal oxide and contain There is the polymer of the unit of following formula 1:
[chemical formula 1]
In chemical formula 1,
A is the alkylidene for being substituted or being unsubstituted, and replaces at least one C of alkylidene chain and can have aromatic hydrocarbon Ring, heterocycle, O, S, C (=O), S (=O) or S (=O)2；
X1For O or S, X2For CR5R6, O or S, n be integer of 1 to 10, p is integer of 1 to 10, and m is integer of 0 to 10；
Y is SO3H、SO3Li、SO3Na、SO3K、SO3Rb or SO3Cs；And
R1To R6It is each independently hydrogen, fluorine, alkyl or fluoroalkyl, however, R1And R2At least one of be fluorine.
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